Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/02—Polyureas

Definitions

• the present invention provides a segmented polyurethan rare having excellent properties.
• PUU PUU continuous molded articles such as fibers and tapes, and a method for producing the same. More specifically, the present invention relates to a PUU continuous molded article having a higher initial stress, a higher elongation and a higher strength than a continuously formed polyurethane-rare molded article obtained by a conventional method. Further, the present invention relates to an improved method for producing a PUU continuous molded product suitable for producing a PUU continuous molded product having a small fineness (a thin film in the case of a tape or the like) at a high production rate.
• Background art
• Polyurethane has expanded into a wide range of fields, including forms, adhesives, paints, elastomers, synthetic leather, and textiles, and has produced many useful products.
• PUU elastic fiber which requires particularly high elasticity, is used as a rubber substitute for stretch stockings such as pantyhose, foundations, socks, and recently, such as disposable diapers. It is used in a wide range of fields.
• the stress (initial stress) at 100% elongation is relatively high ( 0.06 to 0.09 g Zd), the breaking strength is high (1.0 g Zd or more), but the breaking elongation is not so large (500 to 700%), and A type in which stress rises sharply at an elongation of about 400%. Consumers feel excessive tightening when wearing products of this type of fiber (PUU elastic fibers obtained by dry and wet methods).
• a two-step method is generally used to obtain a polyurethan-rare solution (undiluted solution) for spinning that can be used in the dry method and the wet method.
• a diisocyanate component and a diol component are reacted in a molten state to produce a molten prepolymer having an isocyanate group at each end, and then N, N— Dimethyl acetate amide N, N—Dissolved in a solvent such as dimethylformamide to obtain a prepolymer (hereinafter abbreviated as PUP) solution (melt synthesis method)
• PUP prepolymer
• the prepolymer is reacted in a solvent to obtain a prepolymer solution (solution synthesis method), and then, in a second step, the prepolymer is converted to a fatty acid as described in US Pat. No. 2,929,804.
• the solvent is evaporated in a heated spinning tube, and in the wet method, a coagulation bath is used. It is formed into PUU elastic fiber by coagulation inside.
• a PUP is prepared by a fusion method containing no or very little solvent, and this PUP is directly dissolved in a reaction solution containing polyamine.
• This is a simple method of forming into a filament while becoming rare.
• other spinning methods have the advantage of being practically difficult to implement, with the ability to select a wide range of PUU compositions.
• the polymer in the dry method, the polymer must be soluble in the solvent. Therefore, the polymer composition is limited.
• the prepolymer is directly polymerized without being dissolved in a solvent, and thus there is no such restriction. By drastically changing the chemical structure, it has the potential to improve the weather resistance, yellowing resistance, and chlorine resistance, which have been said to be the drawbacks of PU U elastic fibers.
• reaction spinning method examples include US Pat. No. 3,115,384 and US Pat. No. 3,387,071.
• U.S. Pat. No. 3,387,071 states that prepolymers are synthesized by a melt synthesis method, and then the molten prepolymers are directly dissolved in a solution of diamine, a chain extender. It describes a method of discharging and winding while obtaining polyurethan rare.
• PUU elastic fibers obtained by the conventional reaction spinning method have the following problems. (1) First, the resistance of the reaction solution is large and it is difficult to increase the spinning speed. In the prior art, the polyamine bath is substantially stationary.
• the take-up speed exceeds a certain speed, the PU yarn in the forming process receives a large amount of liquid resistance, deteriorates the physical properties, and eventually cuts.
• the spinning speed can be secured only to about 60 to 70 mZ.
• the amount is 500 to 100 mZ.
• PUU elastic fibers produced by the conventional reactive spinning method have high elongation at break but extremely low initial stress (about half that of PUU elastic fibers produced by the dry method), resulting in lower product quality. It is. For this reason and because it is difficult to produce PUU elastic fibers with a fineness of (2), the use of PUU elastic fibers by the conventional reaction spinning method has been limited.
• processing unevenness As a result, there arises a problem that the elongation of the PUU elastic fibers in the fabric structure fluctuates from site to site and becomes apparent as unevenness of the fabric quality (hereinafter collectively referred to as processing unevenness). This is why the initial stress is important in PUU elastic fibers. What is the minimum stress required to remedy this problem? 111; 0 when the ⁇ -fiber is stretched 100% 0.6 to 0.07 g / d or more.
• the present invention solves the above-mentioned problems (1) to (3) of the conventional reaction spinning method and provides PUU fibers and tapes having a high initial stress, a high breaking strength, and a high breaking elongation.
• PUU fibers and tapes having a high initial stress, a high breaking strength, and a high breaking elongation.
• PUU fibers and tapes having a high initial stress, a high breaking strength, and a high breaking elongation.
• PUU fibers and tapes having a high initial stress, a high breaking strength, and a high breaking elongation.
• FIG. 1 is a schematic view showing one example of a continuous molded article manufacturing apparatus used in the present invention.
• FIG. 2 is a schematic view of an example of an apparatus for separating a reaction solution and a continuous molded article used in the present invention.
• FIG. 3 is a schematic view showing another example of the continuous molded article manufacturing apparatus used in the present invention. Disclosure of the invention
• birefringence in the non-tension state is 1 0 X 1 0- 4 or more on 8. 0 X 1 0 -. No greater than 4, 1 0 0% elongation during the crosslinking point density ( N 1 0 0) Power 5.0 x 10 26 / m 3 or more, crosslink density at 400% elongation (N 400) Force 4.0 X 10 26 to 3.0 xi 0 27 / m 3, the crosslinking point density at break (N t) Chikaraku 1.
• the PUU continuous molded article of the present invention is a molded article having sufficiently large initial stress, rupture strength, and rupture elongation, and having a small rise in stress in a middle elongation range, it is possible to provide a fabric with less processing unevenness. In addition, it is possible to provide a product having excellent adhesion without excessive tightening feeling when worn.
• examples of the continuous molded article of the present invention include fibers and films.
• the present invention will be described using fibers as an example. The same applies to films and other continuous molded articles.
• PUU elastic fibers are block copolymers consisting of soft segments that exhibit elasticity and hard segments that function as cross-linking points, and have an amorphous content of 85% by weight or more. It is composed of polymers. Therefore, the PUU elastic fiber has a low stress in a low elongation region before it is subjected to a large deformation under tension to exhibit entropy elasticity. According to the classical rubber elasticity theory, the stress ( ⁇ ) at the elongation (s) is (1
• the crosslinking point density is the number of crosslinking points dispersed in a unit volume of the PUU elastic fiber.
• CT N k T ( ⁇ 2 - 1 / ⁇ ) (1)
• k represents Boltzmann's constant.
• T is the measured temperature.
• Stress is the elongation percentage; the strength at I is divided by the cross-sectional area at the time of elongation (unit: N / m 2 ).
• the cross-sectional area of the PUU fiber at a certain elongation was determined on the assumption that this fiber was Poisson-deformed. For example, when the elongation is 100% and 400%, the cross-sectional area is half and one-fourth of the non-elongation, respectively.
• the stress (initial stress) and the breaking strength when PUU fiber is stretched by 100% are calculated by dividing the stress (TS) under each condition into the initial cross-sectional area as in general fiber strength. Indicated by the value divided by.
• T S and ⁇ are as follows.
• T S CT A. / (D '; 1)
• N N hard + N crysta 1 + N en »ang. (3)
• an extension test is performed at 20 ° C., an initial length of 50 mm, and an extension rate of 100% / min. From the measured values of stress at 100%, 400% and elongation at break and the cross-sectional area of the fiber at that time, the crosslink density determined by the formula (1) was calculated at 100% elongation.
• the crosslink density (N100), the crosslink density at the time of 400% elongation (N400), and the crosslink density at the time of breaking (Nt) were determined. However, Nt is not necessarily proportional to the breaking strength obtained from equation (2).
• Example 6 As can be seen from the comparison between Example 6 and Comparative Example 2 described below, even when the PUU fiber of Example 6 has both higher breaking strength and elongation at break, the PUU elasticity of Comparative Example 2 is higher.
• the Nt of the fiber may be larger.
• the structural characteristics of the PUU fiber of the present invention are shown, and it is shown that the characteristics can be defined by the crosslinking point density (N).
• PUP reacts with polyamine to form high molecular weight polyurethane urea (PUU) and, at the same time, is converted into a fiber to form PUPU fibers.
• PUP polyurethane urea
• the PUP molecular chain temporarily assumes an oriented (flow-oriented) state, but relaxes immediately due to its small molecular weight. Therefore, the manufactured PUU fiber shows a low birefringence.
• the urea bond having a large interaction forms an aggregate (hard segment block), which acts as a crosslinking point.
• P UP preferably used in the present invention is
• the bonding strength of each block is not yet sufficient, so that an appropriate dispersion occurs in the yarn length direction, which results in the cross-link density (N hrd ). Since the crosslinking point density (N 100) of the PUU fiber of the present invention at 100% elongation is substantially equal to N hard , the stress (initial stress) at 100% elongation increases. . On the other hand, when the flow orientation cannot be applied due to the liquid resistance during the reaction spinning as in the conventional chemical reaction spinning method, the Nhard is small and the initial stress is low. On the other hand, N hard of the dry spinning PUU elastic fiber shows a relatively large value. The reason is that the hard segment in the polymer solution is hardly soluble in the solvent, and the hard segment already aggregates in the solution and forms a considerable amount of crosslinking points. Because.
• the change in the crosslink point density when the PUU fiber of the present invention is stretched by 100% or more is slightly complicated.
• the crosslink density does not always increase monotonically with elongation.
• the crosslinking point density (N 400) at an elongation of 400% may be smaller than the crosslinking point density (N 100) at an elongation of 100%.
• N 100 crosslinking point density
• the hard segment cross-linking point of the PUU fiber of the present invention is, as described above, a hard segment block in addition to the hard segment block between the urea groups.
• the hard segment block dissociated between different kinds of blocks effectively acts as a support point, and thus has an elongation of 6%. From around 0%, oriented crystallization of the soft segment begins to occur gradually, and at the same time, entanglement of molecular chains starts, Nt increases, and as a result, high breaking elongation and high breaking strength are obtained. Is expressed.
• the characteristics of the PUU fiber of the present invention having an elongation of 0% (no tension) are defined by the birefringence.
• the birefringence in a non-tension state is 1 0 X 1 0 -. 4 above, 8. 0 X 1 0 - 4 or less.
• the birefringence of unstretched PUU elastic fibers is much lower than that of other synthetic fibers.
• the value of birefringence of PUU elastic fiber other than the PUU fiber of the present invention, a dry spinning method is 1. 0 X 1 0- 2 mm, about teeth in existing reaction spinning 0 X 1 0- 3 .
• PUU fiber of the present invention is obtained by molding at high speed, .DELTA..eta even the case 8. 0 X 1 0 - does not exceed 4.
• the PUU fiber of the present invention having such ⁇ has a breaking elongation of 500% or more, a high initial stress and a breaking strength.
• PUU fibers with ⁇ less than 1.0 X 10 — 4 have high breaking elongation Despite the degree, initial stress and breaking strength are poor.
• the PUU fiber of the present invention has an N 100 force of 5.0 X 10 2 Vm 3 or more, an N 400 force of 4.0 X 10 26 to 3.0 xl 0 27 / m 3 , N t Chikaraku 1. is 6 X 1 0 27 / m 3 or more. If the value is less than 5.0 ⁇ 10 26 / m 3 , the initial stress is small and the practicability is poor, as determined from equation (2). N t is 1. 6 X 1 0 27 / m small breaking strength is less than 3.
• PUU fibers of the present invention those having a particularly large N 100 are found in PUU fibers having crystallinity in an unstretched state.
• This fiber has an extremely large N ⁇ ystal even in the low elongation range due to the crystallinity of the polyol in the unstretched state.
• Elongation initial time of the crosslinking point density (N 1 0 0) 1 for contribution of Yoko. 0 x 1 0 27 / m 3 a exceeds the initial stress that put the elongation 1 0 0% 0. 1 g / It becomes PUU fiber exceeding d.
• the PUU fiber of the present invention not only the absolute value of the crosslinking point density (N) but also the relative value between N100 and N400 is important.
• the PUU fiber of the present invention exhibits characteristic values of N400 / N100 and 0.9 to 3.0. This value is very low compared to 2-3 for PUU elastic fiber produced by dry spinning. Further, N 400 / N 100 of the PUU elastic fiber by the conventional reaction spinning method is about 1.4 to 1.8, and N 100 is 3.5 X 10 26 / m 3 , N t is about 1.1 ⁇ 10 27 Zm 3 .
• N 400 to N 100 clearly characterizes the PUU fibers of the present invention.
• N 100 is not less than 5 ⁇ 10 26 / m 3 and N 400 / N 100 is 0.9 to 1.3, the initial stress is high and in the middle elongation range. The rise of stress is small.
• N 400 / N 100 of the PUU elastic fiber obtained by the conventional reaction spinning method is close to the PUU fiber of the present invention, but N 100 and Nt are smaller than the PUU fiber of the present invention.
• N t of PUU fiber of the present invention is usually 3. 0 ⁇ 4. 0 x 1 0 27 / m 3 (1 to the breaking strength. 2 ⁇ 1. 5 g / d), the conventional dry spinning method is comparable to that according PUU elastic fibers by, but preferred case 5. 0 X 1 0 27 / m 3 to reach even (1.5 equivalent to the breaking strength of at least GZD), the PUU elastic fibers by dry spinning Among them, it is comparable to those in the highest strength category.
• the PUU fiber of the present invention exhibits such a unique elongation dependence of the crosslinking point density. In the middle elongation region, the rise of stress is remarkably small, and high breaking strength and high breaking elongation are realized.
• the PUU fiber of the present invention can provide a fabric with less processing unevenness, and can provide a processed product having good adhesion (fitness) without losing its shape even when worn and having no excessive feeling of tightening. It has excellent characteristics that can be provided.
• the PUU fiber of the present invention usually has an initial stress of 0.07 to 0.1 g / d, a breaking strength of 1.2 g / d or more, and a breaking elongation of 700 to 100%.
• the initial stress is 0.1 g / d or more
• the breaking strength is 1.5 gZd or more
• the breaking elongation is 700 to 900%.
• the second invention of the present invention is obtained from a polyisocyanate and a polyol.
• a liquid polyurethane prepolymer having at least two isocyanate groups at its ends is discharged from a molding nozzle at a linear discharge speed Ls, and the discharged polyurethane prepolymer is discharged.
• This is a method for producing a continuous polyurethane molded article characterized by taking off.
• Polyurethane prepolymers having an isocyanate group at both terminals obtained by the reaction of a polyisocyanate and a polyol used in the present invention are aliphatic or alicyclic. Alternatively, at least one kind of polyisocyanate selected from an aromatic polyisocyanate and a polyol may be in a stoichiometric excess of an isocyanate group. Below, it is a liquid prepolymer having an isocyanate group at the terminal obtained by reaction according to a conventional method. As for PUP of the present invention, there is basically no limitation on the combination of polyisocyanate and polyol as long as it is a liquid that can be discharged from a molding nozzle.
• polyisocyanate used in the present invention examples include aliphatic di- and tri-isocyanates, aromatic di- and tri-isocyanates.
• aliphatic di-sodium are 1,4-tetramethyl-di-soyate, 1,6-hexadi-methyl-di-soyate, 1,1 and 2—dodecane di-so-cynate 1, 6, 11- ⁇ ⁇ ⁇ 4 4 4 4 4 4 — — — — 4 4 — — — 4 — 4 — 4 4 — —.
• Cyanate, 3, 3 Dimethyl pentane 1,5-diisocyanate.
• cycloaliphatic diisocyanates such as 1,3- and 1,4-cyclohexanediisocyanates.
• aliphatic triisocitanes include, for example, lysine ester triisocitane, 1,3,6—hexamethylene triisocynate, 1,8—diisocyanate
• Aliphatic trisodium citrates such as trioctane octane and triphenylmethanthyl trisocanates and tris (isothienyl phenyl) trifos
• Any use of these trisockets in combination with the above-mentioned jisocyanate is acceptable.
• aromatic di- and tri-isocyanates those in which the isocyanate group is directly connected to the benzene nucleus and the two isocyanate groups are bonded to the para position are preferred.
• Aromatic diisocyanates in which two isocyanate groups are bonded in asymmetric positions for example, 2,4—tolylene diisocyanate ⁇ 1,3—phenylene isocyanate
• the power to obtain the PUU fiber of the invention is not preferred because the physical properties of the PUU fiber are inferior to those from the para-linked aromatic diisocyanate.
• aromatic diisocyanates examples include 1,4-phenylenediocyanate, 4,4 'diphenyl methanediisocyanate (MDI), 4,4, diphenyl diisocyanate.
• MDI 4,4 'diphenyl methanediisocyanate
• aromatic diisocyanates particularly preferred are the PUP viscosity and the physical properties of PUU fibers such as 4,4'-diphenylmethanediisocyanate (MDI).
• MDI 4,4'-diphenylmethanediisocyanate
• Trif X Lumentant litho- nates, tris (iso- gen-to-fan), pho- to-folio etc. can be used.
• Polyols used in the present invention preferably have a number average molecular weight of 800 to 600 and a melting point of 60 ° C. or lower, but are not limited thereto.
• examples of such polyols include polyether polyols, polyester polyols, polylactone polyols, and polycarbonate topoliols.
• polymethylsiloxane polyol and unhydrogenated or hydrogenated polybutadienepolyol can also be used.
• polyether polyol examples include polyoxytetramethylethylene glycol (PTMG), poly (1,5-pentanediol), and polyethylene glycol. These polyols may be chain-like or branched. Polyester polyols include one or more dibasic acids such as oxalic acid, succinic acid, glutaric acid, fumaric acid, sebacic acid, maleic acid, itaconic acid, adipic acid, and malonic acid. And diols such as ethylene glycol, propylene glycol, butanediol, hexanemethylenglycol, cyclohexanedimethanol, and the like.
• Polyesters having a carboxyl group at the end obtained by such a method include polyether diols such as, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylen glycol, and polyoxypentamethylen glycol. Use the product obtained by the reaction Is also possible. You can also use natural polyester polyols ⁇ s.
• Polylactone polyols include propylene glycol and hydroxycarboxylic acid obtained by ring-opening polymerization of ⁇ -caprolactone and the like. Examples thereof include those obtained by reacting a diol such as butanediol, and those obtained by reacting a polymer diol such as polyoxytetramethylene glycol or polyoxypentamethylene glycol.
• Polycarbonate topolol includes alkylene carbonates and 1,4-butanediol, 1,3-pentanediol, 1,5-pentanediol, 1,6-hexanediol, etc. (Butane-1,4—carbonate diol), poly (pentane1,5—potassium diol) and poly (hexane-1,1,6—carbonate) Diols) and their copolymers and polycarbonate diols obtained from mixtures thereof.
• polyester polyols and polyester polyols are susceptible to mold embrittlement, and polycarbonate carbonate polyols have high melt viscosities and are difficult to handle.
• Polyoxytetramethyllene glycol (PTMG) is particularly preferred in view of the chemical stability and tensile properties of PUU fiber.
• Ethylene glycol 1,2-propanediol, 1,4-butanediol, 2-methyl-1,1,4-one, in order to adjust the urethane group concentration in the PUP to obtain desired physical properties.
• Aliphatic diols such as butanediol, neopentyl glycol, 3-methyl-1,5-pentanodiol; alicyclic diols such as cyclohexanediol and tricyclodecandimethanol;
• Low molecular weight diols selected from aromatic-containing diols such as 1,4-bis (/ 3-hydroxoxy) benzene can also be added.
• the stoichiometric ratio of the polyisocyanate to the polyol is in the range of 1.1 to 2.5 depending on the viscosity and molecular weight of PUP, the tensile properties of PUU fiber, and the heat resistance. Preferred from.
• a viscous liquid having a PUP viscosity of about 100 to 600 voise (20 ° C.) is preferred.
• ketones such as acetone, methylethyloketone, methylinolaysobutinoleketone, N, N—dimethyl acetate amide N, N—dimethylethylforma
• Amides such as amides, ethers such as tetraethyl ether, dimethyl ether, dimethyl sulfoxide and the like may be added in small amounts to the PUP.
• stabilizers such as antioxidants, anti-yellowing agents, and ultraviolet absorbers may be added to PUP.
• the polyamine-containing solution of the present invention (hereinafter, referred to as a reaction solution) is a reaction between diamine and an isocyanate group in the PUP which is inert to the diamine and the amine compound.
• a reaction solution is a reaction between diamine and an isocyanate group in the PUP which is inert to the diamine and the amine compound.
• the solvent is used as an amine diluent or viscosity modifier. Solvents are more preferred if they have the effect of promoting the diffusion and penetration of the amine into the PUP.
• polyamine which is a chain extender for PUP
• known aliphatic, alicyclic and aromatic polyamines can be used. Specifically, for example, ethylenediamine, propylenamine, 1,3—prono, and so on. 1,2-butylenediamine, 1,3-butylenediamine, 1,4 butyldiamine, 1,5—hexanediamine, isobutylene Diamine, 1, 6 — hexanediamine, cyclohexanediamine, isophoronediamine, pyrazine, 2 —methylbiperazine, phenylenediamine, Tri-diamine, m-xylylene diamine, p-xylylene diamine, 3,3, -dichloro-1,4,4'-biphenyldiamine 2,6—diaminopyridine, 4,4'-diaminodiphenylmethane, hydrogenated m-phenylenediamine, p-phenylenedi
• low molecular weight triamine such as tris (2-aminoethyl) amine.
• Polyoxyalkylenepolyamine having a molecular weight of 400 or more, for example, trade name "J Polyamines such as “effamine” (Huntsman) can also be used.
• Monoamine compounds such as methylamine, ethylamine, propylamine and its isomers, butylamine and its isomers, and getylamine can be used as the polymerization degree regulator.
• Asymmetric hydrazine such as dimethyl hydrazine and getyl hydrazine can also be used as the monoamine.
• ethylen glycol, 1,4-butanediol, 1,3-butylene glycol, and prothylene glycol are used as solvents for diluting polyamine.
• Aromatic hydrocarbon Classes such as benzene, toluene, 0-xylene, p-xylene, m-xylene, mixed xylene, ethylbenzene, 1,3,5—trimethylbenzene, propylbenzene, isopropylbenzene And butylbenzene. These mixed solvents may be used.
• a surfactant or the like may be added for the purpose of promoting the diffusion and penetration of the amine into the PUP.
• the first essential aspect of the production method of the present invention includes, after discharging PUP from a molding nozzle at a discharge linear velocity Ls, a reaction liquid flowing at an average flow velocity Vf in the same direction as the PUP travels.
• Ls ⁇ Vf is satisfied, and the isocyanate group and polyamine are reacted to extend the PUP chain to form PUU. While taking over at a take-up speed Vt greater than Vf.
• the purpose of the production method of the present invention is to make the reaction solution move at a speed higher than the speed of the yarn during the process of forming PUP and PUU fibers (hereinafter referred to as PUU yarn), and to reduce the liquid resistance.
• PUU yarn PUP and PUU fibers
• the average flow velocity V f defined in the present invention is a value obtained by dividing the amount of the reaction solution flowing out of the reaction bath outlet by the cross-sectional area of the reaction bath.
• the cross section of the reaction bath is a circular tubular path
• the central part of the tubular path has a flow velocity almost twice V f.
• the present invention requires that V t ⁇ V f.
• Ls ⁇ Vf ⁇ Vt is better for PUU fiber toughness (strength X) so that fibers and tapes, etc. can exhibit high strength and elongation by forming under appropriate tension. Elongation) is improved, and these conditions are more preferable in terms of spinning stability, and the PUU filaments do not break.
• the PUP completes the chain extension ( ⁇ rare) reaction instantly (on the order of tens to hundreds of microseconds) upon contact with the reaction solution.
• urea reaction basically occurs from the surface of the PUP, and the surface layer first changes to a solid. Therefore, the discharged PUP develops stress corresponding to the take-off speed only after the solidification of the surface layer has started, and if it moves along with the flow of the reaction solution during a very short period before that, Conceivable. In this concomitant period If L s> V f, PUP is not preferred because it substantially receives liquid resistance from the reaction solution.
• the PUP is accelerated until it reaches the take-off speed Vt simultaneously as the whole becomes rare, and is formed into a PUU filament while being appropriately oriented while repeating molecular chain orientation and relaxation.
• Vt the take-off speed
• V f the reaction liquid around the PUU filament that passes while being accelerated in the reaction bath is locally accelerated along with the PUU filament, so that the reaction solution is substantially resistive. Not be. Therefore, even under the condition of Vt >> Vf, the cutting of the filament does not occur, and the filament having a fine size can be taken up at high speed.
• Vt As the take-up speed Vt increases or the single fineness decreases, it becomes more difficult to separate the PUU thread from the reaction solution.Therefore, in order to continuously pull the thread under tension, It is preferred that V t ⁇ V f.
• the discharged PUP can always come in contact with fresh reaction solution, so that the amount of the reaction solution can reduce the amount of the isocyanate group in the PUP.
• the minimum required is sufficient. As a result, it is possible to significantly reduce the liquid resistance.
• the polyurethan urea is withdrawn from the fluidized bath at a withdrawal speed of Vt1, and then with a withdrawal speed Vt of Vt ⁇ 1.5 Vt1. This is a method for producing a PUU continuous molded body.
• the process of transition from the PUP to the PUU filament occurs under almost no tension, resulting in deformation without structural failure.
• the relaxation of the polyurethan-rare molecular chain takes precedence over the orientation
• the hard segment has a high molecular weight
• the hard segment has an appropriate dispersion.
• the PUU thread that has left the reaction bath passes through the entire process without undergoing undue deformation.
• N 1 0 0 is high
• PUU fiber of extremely high invention N t is obtained. That is, the initial stress is 0.0 from 7 to 0.1 8 / / (1, breaking strength elongation at break at 7 0 0-1 0 0 0% 1. is a this increase to more than 2 g / d it can.
• a second preferred embodiment of the invention is characterized in that the polyurethan is withdrawn from the fluidized bath at a rate of Vtl and then with a rate Vt of Vt> 1.5 Vt1. This is a method for producing a continuous polyurethane molded product.
• the method of the present invention is particularly effective for obtaining a PUU fiber of the present invention having a high initial stress (that is, an initial elastic modulus). If Vt is at least 1.5 times Vtl, the initial stress will be even higher.
• the delta eta of PUU fiber obtained is the upper limit of the present invention 8. 0 X 1 0- 4 close to, elongation 1 0 initial stress as defined 0 percent from 0.1 to 0.2 5 g / d, which is the same as the PUU elastic fiber obtained by the conventional chemical reaction spinning method (in some cases, it can reach 5 times.
• the elongation at break is more than 500% and the breaking strength is 1.
• V t and L s depends on the PUP used, but preferably does not exceed 30.
• the method of the present invention high-speed spinning of about 10 times or more as compared with the conventional reaction spinning method is possible, and a spinning speed comparable to the dry method can be achieved.
• the initial stress is sufficiently larger than that of the PUU elastic fiber of the conventional chemical spinning method, and reaches about 5 times in a preferable case.
• the breaking elongation is increased to 700-10000%, and the breaking strength is comparable to the highest strength PUU fiber obtained by the dry spinning method.
• the PUP (3) discharged from the molding nozzle (2) incorporated in the nozzle holder (1) is sealed and contains a polyamine-containing reaction liquid.
• the tubular path body (5) whose diameter is sharply reduced to a tubular form, and then polyamine.
• the PUU filament is released into the gaseous atmosphere at the outlet of the pipe in the tubular channel (6), and is taken off after being separated from the reaction solution. .
• the reaction solution is injected into the main body of the manufacturing apparatus (8) at the reaction solution inlet (7) and passes through the distribution plate (9). Then, it is led to the tubular road body (5) from the inlet (4) of the flared tubular pipe 8, and flows out from the body outlet (6).
• the flared tubular passage inlet (4) and the tubular passage main body (5) are filled with the reaction solution and the reaction solution can be forcibly supplied, so that the flow rate of the reaction solution is higher than that in the naturally flowing state. Can be moved with.
• the method of separating the PUU filaments and the reaction solution that have exited the tubular channel is particularly important in the case of producing PUU fibers of fine size.
• the following three methods are used. Preferable, but not limited.
• the first is a method in which the PU U thread that has exited from the tubular outlet (6) is caused to run in air or an inert gas, to make the reaction liquid into droplets, and to separate the reaction liquid from the P U U thread.
• the running distance varies depending on the surface tension of the reaction solution and the like, and thus may be appropriately determined by experiments.
• a short pipe orifice is installed between the outlet of the tubular path and the take-up roll, and the orifice is passed through the PUU thread to allow excess reaction liquid to overflow. It is a method of separating. It is more effective when combined with the first method.
• a method is used in which the outlet of the tubular road (for example, the portion (6) in Fig. 1) is turned at an angle 01 and separated. It is preferable that ⁇ 1 is 120 to 150 degrees.
• the cutout angle ⁇ 2 of the cutout at the outlet is preferably (180-61) degrees. It is preferable to increase S 1 as the reaction solution flow rate V f increases.
• the PUP discharged from nozzle 2 passes through the air gap of A, then comes into contact with the reaction solution at the reaction solution interface B, and has a tube-shaped tube with a sudden reduction in tube diameter. It will be introduced at the road entrance (4). Next, it is led to the tubular channel (5) and undergoes chain elongation reaction with polyamine to form a PUU filament, which is then released at the outlet of the tubular channel, It is separated from the reaction solution and taken off.
• the polyamine-containing reaction solution is injected from the reaction solution inlet (7) into the manufacturing apparatus body (8), passes through the distribution plate (9), and maintains the liquid level regulated by the overflow pipe (10). While flowing into the entrance of the tubular road (_4).
• the reaction solution and the PUP come into contact at liquid level B for the first time. In the steady state, the reaction solution must fill the entire tubular channel.
• the reaction liquid supplied to the tubular path is considerably lower than the liquid flow rate in the free-falling state with the same head length due to the pressure loss according to the material, structure and properties of the reaction liquid, etc. This is convenient for reducing the flow rate of the reaction solution in the tubular channel to a desired speed.
• the PUP can be cooled or heated at the air gap, or can be preliminarily brought into contact with the reactant.
• the PU thread coming out of the tubular path is taken under predetermined conditions. Then, if necessary, dry the excess amine and the solvent for diluting the amine directly, or wash with water, etc., and dry with hot air. Can be Additives and oils may be applied before drying. Excessive heat can be applied to the PU filaments during drying for annealing. Annealing is effective because it can increase strength and elongation to improve toughness, and can induce a chemical reaction such as an amino exchange reaction.
• Example 1
• a PUP consisting of 4,4'-diphenylmethandiisocinate (hereinafter referred to as MDI) and polyoxytetramethylen glycol (hereinafter referred to as PTMG) was synthesized as follows. 53.8 g of MDI (molecular weight 250.3) was weighed into a 500 cc Seno- ° flask and stirred in nitrogen gas at 50 ° C until the MDI was completely dissolved.
• MDI 4,4'-diphenylmethandiisocinate
• PTMG polyoxytetramethylen glycol
• PUP-2 composed of MDI, PTMG, and 1,4-butanediol (hereinafter, referred to as 1,4BD) was synthesized as follows.
• PUP-3 consisting of MDI, PTMG and ethylenediamine (EDA) was synthesized as follows.
• MD I and PUP-4 composed of PTMG with a molecular weight of 85 (PTMG850) and PTMG with a molecular weight of 300 (PTMG3000) were synthesized as follows.
• IPA isopropyl alcohol
• the reaction solution (30 ° C) having a falling velocity is guided to a tubular path, and formed into a PUU filament while passing through the tubular path.
• Three tubes at a speed of 500 and 100 OmZ respectively were continuously taken through a washing step, a drying step, and an oiling step at 550 and 110 m / min, respectively, and finally taken out at 500,000 m / min. It was wound at a speed of 100 Om / min.
• the PUU fibers wound at 500 Om / min and 100 OmZ are referred to as Example 5 and Example 6, respectively.
• Table 1 shows the tensile properties of Examples 5 and 6.
• PUU elastic fiber of the reactive spinning method sold in Reference Example 1 was used, and commercially available dry method was used in Reference Example 2.
• the tensile properties of the PUU elastic fiber obtained in the above are also shown.
• Example 56 the initial elastic modulus was high, and the properties as an excellent PUU elastic fiber having high strength and elongation were obtained.
• the reaction solution (30 ° C) having a flow velocity of 600 m / min was guided to the tubular path, and was formed into PUU filaments and passed through the tubular path.
• the PUU filaments are continuously taken at 200, 250, 300, 400, and 800 m / min (Vt), respectively, and then washed with water and dried. After that, each was rolled at a constant speed to produce a total of five PUU samples.
• V t is 20 Samples of 0, 250, 300, 400, and 800 mZ are referred to as Examples 15, 16, 17, 17, 18, and 19, respectively. Table 4 shows the tensile properties of these examples. Examples 17 to 19 had crystallinity in the non-stretched state and had a high initial elastic modulus.
• Example 15 Example 16 Example 17 Example 18 Example U9 Fineness (denier) 48 38 32 24 12
• the PUU fiber of Example 20 had a fineness of 5 denier and was a very thin fiber as the PUU elastic fiber. Furthermore, it is almost impossible to form PUU elastic fibers having a denier of 5 denier in monofilament at the high spinning speed as in the present invention by the conventional reaction spinning method or dry spinning method. .
• PUP-1 is an air-gap type with a tubular section with a rectangular cross section of 5 mm in width, 8 mm in length, and a tubular section of 400 mm in length.
• wound at 40 Om / min through water washing, pre-drying, and oil application.
• a PUP film was obtained from the pre-polymer of PUP-1 as follows.
• the closed tubular passage has a rectangular cross section with a pipe cross section of 4 mm in width, 8 mm in length, 1.5 mm in cross section in outlet, 8 mm in length, and a tubular path length of 5 OO. mm.
• PUP-1 is followed by ethylene amine z isoprono.
• a reaction solution (30 ° C) having a flow velocity of 0 mZ
• the reaction liquid (30 ° C) was introduced into a tubular path, and formed into a PUU filament, and passed through the tubular path. It was pulled out to the outlet of the tubular road by the snub roll composed of the rolls.
• the PUU thread was continuously taken up at 880 m / min through the washing step, drying step, and oiling step, and finally wound up at 800 m / min. .
• the fineness was 108 denier.
• Table 5 shows the tensile properties of the fibers of Example 23.
• Example 24 Using a reaction solution (30 ° C) with a falling velocity, it is guided into a tubular path, and formed into a PUU thread, passed through a tubular path, and consists of three rolls at a speed of 800 m / min. It was pulled out to the exit of the tubular road by snabrol. Further, the PUU filament was continuously taken out at a rate of 88 Om / min through a washing step, a drying step, and an oiling step, and finally wound up at a rate of 80 OmZ. The fineness was 108 denier. Table 5 shows the tensile properties of the fibers of Example 24. As in Example 23, there was a tendency for higher initial stress and higher breaking strength as compared to the PUPU fiber from PUP-1.
• this PUU thread is subjected to a water washing step, a drying step, and an oiling step, and
• Example 25 shows the tensile properties of the fiber of Example 25. In Example 25, not only the initial stress, the breaking strength, and the breaking elongation were high, but also the fibers tended to be balanced among the three.
• the PUU continuous molded article of the present invention is a molded article having sufficiently large initial stress, rupture strength, and elongation at break, and having a small rise in stress in a middle elongation range, so that a cloth with less processing unevenness is provided. It is possible to provide a product having excellent adhesion without excessive tightening feeling when worn.
• the production method of the present invention has made it possible to produce a PUU continuous molded body having a wide fineness, which is difficult to achieve by the conventional reaction spinning method and dry spinning method, at a high spinning speed comparable to the dry method.

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